WO2011090705A2 - Polyarylene polymers and processes for preparing - Google Patents

Polyarylene polymers and processes for preparing Download PDF

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Publication number
WO2011090705A2
WO2011090705A2 PCT/US2010/062199 US2010062199W WO2011090705A2 WO 2011090705 A2 WO2011090705 A2 WO 2011090705A2 US 2010062199 W US2010062199 W US 2010062199W WO 2011090705 A2 WO2011090705 A2 WO 2011090705A2
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polymer
give
mmoles
solution
mixture
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PCT/US2010/062199
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WO2011090705A3 (en
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Mark F. Teasley
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E. I. Du Pont De Nemours And Company
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Priority to KR1020127019864A priority Critical patent/KR20120125266A/ko
Priority to JP2012547230A priority patent/JP5701903B2/ja
Priority to EP10844255.9A priority patent/EP2519554B1/en
Publication of WO2011090705A2 publication Critical patent/WO2011090705A2/en
Publication of WO2011090705A3 publication Critical patent/WO2011090705A3/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/14—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/516—Charge transport ion-conductive

Definitions

  • the present invention is directed to polyarylene polymers useful as engineering polymers, and to processes and monomers for use in preparing the polymers.
  • High performance polymers are a fast growing portion of the engineering polymers market. These polymers offer excellent
  • thermoplastic HPP are either semi-crystalline or amorphous with the former typically offering superior chemical and abrasion resistance and the latter superior thermal resistance and mechanical toughness.
  • semi- crystalline HPP are polyphenylene sulfide, liquid-crystal polyesters, and polyether ketones, and the most common amorphous HPP are polyether sulfones and thermoplastic polyimides. These polymers are typically filled with glass fiber, carbon fiber, graphite, and other materials as
  • HPP self-reinforced polyphenylene
  • SRP self-reinforced polyphenylene
  • amorphous polymer with many of the attributes of the semi- crystalline polymers.
  • SRP offers a unique combination of tensile properties, abrasion resistance, chemical resistance, and thermal stability.
  • the key to its high performance is the rigid-rod phenylene backbone which makes further fiber reinforcement unnecessary.
  • the polyphenylene backbone can be substituted with phenylketone groups to render it amorphous and allow for thermal processing. For example, Wang and Quirk, Macromolecules, 1995, 28 (10), p.
  • poly(2,5- benzophenone) is thought to be amorphous due to the head-tail disorder introduced in the polymer backbone during polymerization of 2,5- dichlorobenzophenone and that the degree of disorder has an effect on the glass transition temperature (Tg) of the polymer.
  • a sulfone version of SRP such as poly(2,5-diphenylsulfone) (PDS)
  • PDS poly(2,5-diphenylsulfone)
  • One aspect of the present invention is a polymer comprising repeating units of Formula (I):
  • the repeat unit can be referred to as a rigid-rod polyarylene; however it has a higher degree of structural order than typical rigid-rod polyphenylenes by virtue of its symmetrically meta-disubstituted biphenylene structure.
  • bulky aromatic group is meant an aromatic carbocyclic group having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple condensed rings in which at least one is aromatic, (e.g.,
  • the bulky aromatic group can be optionally substituted with a non-reactive group, such as alkyl, other aromatic groups, and other non-reactive functional groups such as ethers.
  • T is phenyl.
  • polymer is intended to include homopolymers, copolymers, and terpolymers.
  • the polymer can have a number average molecular weight (M n ) of at least about 5,000, or at least about 15,000, or at least about 19,000.
  • the polymer can also have a weight average molecular weight (M w ) of at least 80,000, or at least 200,000.
  • the polymer is a homopolymer.
  • the polymer is a copolymer, containing other repeat units.
  • Such other repeat units can maintain the rigid-rod nature of the biphenylene backbone of the polymer comprising repeating units of Formula (I), or can introduce varying degrees of flexibility.
  • Appropriate rigid-rod repeat units can be similar in chemical composition and structure to preserve the physical properties of the polymer comprising repeating units of Formula (I) or can be different to introduce additional properties required for processing and/or for the desired application of the polymer.
  • the polymer can additionally comprise repeating units of Formula (II):
  • T' is a bulky aromatic group.
  • T' is phenyl.
  • These embodiments introduce sufficient head-tail disorder in the phenylene repeat units of the polymer to modify its physical properties while preserving the rigid-rod structure.
  • Polymers comprising repeating units of both Formula (I) and Formula (II) can have a number average molecular weight (M n ) of at least about 5,000, or at least about 9,000, or at least about 60,000.
  • the polymers can also have a weight average molecular weight (M w ) of at least 40,000, or at least 300,000.
  • a suitable monomer to prepare polymers comprising repeating units of Formula (I) is a compound of Formula (IA):
  • T is as described above and X is independently Br or CI, typically CI, and has a higher degree of structural order than typical rigid- rod polyphenylenes by virtue of its symmetrically meta-disubstituted biphenylene structure.
  • a suitable monomer to prepare polymers comprising repeating units of Formula (II) is a compound of Formula (IIA):
  • the polymer comprising repeating units of Formula (I) with repeating units of Formula (II) can be block, random, or alternating copolymers.
  • the monomers of Formulae (IA) and (IIA) may be reacted to form larger monomeric units that are then polymerized alone or with other monomers to form the polymers disclosed herein.
  • a copolymer (-A-) x (-B-) y may be formed by copolymerizing monomer X-A-X with monomer X-B-X, or by forming larger monomer X-A-B-X and polymerizing that monomer. In both cases, the resulting polymer is considered a copolymer derived from monomer X-A-X and monomer X-B- X.
  • the monomers of Formula (IA) and (IIA), and the reactants used to prepare the monomers may be obtained commercially or be prepared using any known method in the art or those disclosed herein.
  • the practical upper limit to the number of monomeric units in the polymer is determined in part by the desired solubility of a polymer in a particular solvent or class of solvents. As the total number of monomeric units increases, the molecular weight of the polymer increases. The increase in molecular weight is generally expected to result in a reduced solubility of the polymer in a particular solvent. Moreover, in one
  • the number of monomeric units at which a polymer becomes substantially insoluble in a given solvent is dependent in part upon the structure of the monomer.
  • a polymer composed of disubstituted biphenylene-based monomers may become substantially insoluble in an organic solvent if the resulting polymer becomes too rigid in the course of polymerization and the biphenylene repeat unit is too structurally regular due to the structure of T.
  • the number of monomeric units at which a copolymer becomes substantially insoluble in a given solvent is dependent in part upon the ratio of the comonomers.
  • a copolymer composed of several rigid monomers may become substantially insoluble in an organic solvent when ratio of disubstituted biphenylene monomeric units to substituted phenylene monomeric units is too large.
  • the selection of polymer molecular weight, polymer and copolymer composition, and a solvent is within the purview of one skilled in the art.
  • the polymerizations as described herein can generally be performed by synthetic routes in which the leaving groups of the
  • carbon-carbon bond-forming reactions are typically mediated by a zerovalent transition metal complex that contains neutral ligands.
  • the zerovalent transition metal complex contains nickel or palladium.
  • complex is meant one or more metal cations together with associated anions and/or neutral ligands.
  • Neutral ligands are defined as ligands that are neutral, with respect to charge, when formally removed from the metal in their closed shell electronic state.
  • Neutral ligands contain at least one lone pair of electrons, a pi-bond, or a sigma bond that is capable of binding to the transition metal.
  • the neutral ligand may also be a combination of two or more neutral ligands.
  • Neutral ligands may also be polydentate when more than one neutral ligand is connected via a bond or a hydrocarbyl, substituted hydrocarbyl or a functional group tether.
  • a neutral ligand may be a substituent of another metal complex, either the same or different, such that multiple complexes are bound together.
  • Neutral ligands can include carbonyls, thiocarbonyls, carbenes, carbynes, allyls, alkenes, olefins, cyanides, nitriles, carbon monoxide, phosphorus containing compounds such as phosphides, phosphines, or phosphites, acetonitrile, tetrahydrofuran, tertiary amines (including heterocyclic amines), ethers, esters, phosphates, phosphine oxides, and amine oxides.
  • the zerovalent transition metal compound that is the active species in carbon-carbon bond formation can be introduced directly into the reaction, or can be generated in situ under the reaction conditions from a precursor transition metal compound and one or more neutral ligands.
  • a zerovalent nickel compound such as a coordination compound like bis(1 ,5- cyclooctadiene)nickel(O)
  • a neutral ligand such as triphenylphosphine or 2,2 ' -bipyridine.
  • a second neutral ligand such as 1 ,5-cyclooctadiene, can be used to stabilize the active zerovalent nickel compound.
  • the catalyst is formed from a divalent nickel salt.
  • the nickel salt can be any nickel salt that can be converted to the zerovalent state under reaction conditions. Suitable nickel salts are the nickel halides, typically nickel dichloride or nickel dibromide, or coordination compounds, typically bis(triphenylphosphine)nickel dichloride or (2,2'-bipyridine)nickel dichloride.
  • the divalent nickel salt is typically present in an amount of about 0.01 mole percent or greater, more typically about 0.1 mole percent or greater or 1 .0 mole percent or greater.
  • the amount of divalent nickel salt present is typically about 30 mole percent or less, more typically about 15 mole percent or less based on the amount of monomers present.
  • the polymerization is performed in the presence of a material capable of reducing the divalent nickel ion to the zerovalent state.
  • Suitable material includes any metal that is more easily oxidized than nickel. Suitable metals include zinc, magnesium, calcium and lithium, with zinc in the powder form being typical. At least stoichiometric amounts of reducing agent based on the monomers are required to maintain the nickel species in the zerovalent state throughout the reaction. Typically, about 150 mole percent or greater, more typically about 200 mole percent or greater, or about 250 mole percent or greater is used. The reducing agent is typically present in an amount of about 500 mole percent or less, about 400 mole percent or less, or about 300 mole percent or less based on the amount of monomer.
  • Suitable ligands are neutral ligands as described above, and include trihydrocarbylphosphines.
  • Typical ligands are monodentate, such as triaryl or trialkylphosphines like triphenylphosphine, or bidentate, such as 2,2'-bipyridine.
  • a compound capable of acting as a monodentate ligand is typically present in an amount of from about 10 mole percent or greater, or about 20 mole percent or greater based on the monomer.
  • a compound capable of acting as a monodentate ligand is typically present in an amount of about 100 mole percent or less, about 50 mole percent or less, or about 40 mole percent or less.
  • a compound capable of acting as a bidentate ligand is typically present in an amount that is about a molar equivalent or greater based on the divalent nickel salt.
  • the bidentate ligand can be incorporated into the nickel salt as a coordination compound as described above.
  • a dihalo derivative of one monomer is reacted with a derivative of another monomer having two leaving groups selected from boron ic acid (-B(OH 2 ) or boronate salt, boron ic acid esters (-BOR2) or (-B(ORO)), and boranes (-BR 2 ), where R is generally a hydrocarbyl group, in the presence of a catalytic amount of a zerovalent palladium compound containing a neutral ligand as described above, such as tetrakis(triphenylphosphine)palladium(0).
  • the reaction mixture should include sufficient water or an organic base to hydrolyze the boronic ester or borane group to the corresponding boronic acid group.
  • the diboronic derivative of a monomer can be prepared from the dihalo derivative by known methods, such as those described in Miyaura et al., Synthetic Communication, Vol. 1 1 , p. 513 (1981 ) and Wallow et al., American Chemical Society, Polymer Preprint, Vol. 34, (1 ), p. 1009 (1993).
  • Suitable accelerators include alkali metal halides such as sodium bromide, potassium bromide, sodium iodide, tetraethylammonium iodide, and potassium iodide.
  • the accelerator is used in a sufficient amount to accelerate the reaction, typically 10 mole percent to 100 mole percent based on the monomer.
  • the reactions are typically run in a suitable solvent or mixture of solvents, that is a solvent that is not detrimental to catalyst, reactant and product, and preferably one in which the reactants and products are soluble.
  • suitable solvents include ⁇ , ⁇ -dimethylformamide (DMF), toluene, tetrahydrofuran (THF), acetone, anisole, acetonitrile, N,N- dimethylacetamide (DMAc), and N-methylpyrrolidinone (NMP).
  • DMF ⁇ , ⁇ -dimethylformamide
  • THF tetrahydrofuran
  • acetone acetone
  • anisole acetonitrile
  • NMP N-methylpyrrolidinone
  • reaction is typically conducted in the absence of oxygen and moisture, as the presence of oxygen can be detrimental to the catalyst and the presence of a significant amount of water could lead to premature termination of the process. More typically, the reaction is performed under an inert atmosphere such as nitrogen or argon.
  • the reactions can be performed at any temperature at which the reaction proceeds at a reasonable rate and does not lead to degradation of the product or catalyst. Generally, the reaction is performed at a temperature of about 20 °C to about 200 °C, more typically less than 100 °C.
  • the reaction time is dependent upon the reaction temperature, the amount of catalyst and the concentration of the reactants, and is usually about 1 hour to about 100 hours.
  • the polymers prepared by the disclosed methods can be recovered according to conventional techniques including filtration and precipitation using a non-solvent. They also can be dissolved or dispersed in a suitable solvent for further processing.
  • the polymers disclosed herein are suitable for use as engineering polymers in applications such as, for example, molecular reinforcement in nanocomposites, mineral-filled and fiber-reinforced composites, injection and compression-molded parts, fibers, films, sheets, papers, and coatings, and can be processed both thermally as is typical for thermoplastic polymers and in solution after dissolving in suitable solvents depending on the requirements of the application.
  • the slurry was treated with 50 % sodium hydroxide solution (130 g) and diluted to 900 mL with water with heating to disperse the precipitated solids.
  • the mixture was cooled to room temperature and the solids collected by vacuum filtration under a rubber dam.
  • the solids were washed with two times with isopropanol (200 mL) and air dried on the filter then dried under vacuum at 100 °C to give 159 g (93 % crude yield).
  • the product was recrystallized from ethanol/water (4:1 ) and dried under vacuum at 150 °C to give 146 g (86 % yield) of 2,5- dibromobenzenesulfonic acid, sodium salt.
  • 1 H NMR (DMSO-d 6 ) 7.42 (dd, 8.4, 2.6 Hz, 1 H), 7.53 (d, 8.4 Hz, 1 H), 8.01 (d, 2.6 Hz, 1 H).
  • the reaction mixture was poured into concentrated hydrochloric acid to precipitate the polymer and the mixture was chopped in a blender to disperse the polymer into particles.
  • the polymer was collected by vacuum filtration using water to wash the polymer.
  • the polymer was washed with concentrated hydrochloric acid followed by water.
  • the damp polymer was washed with cyclohexane followed by methanol and dried in a vacuum oven at 70 °C under nitrogen purge to give 1 .32 g (88 % yield) of poly[(2,2'-bis-benzenesulfonyl-4,4'-biphenylene)].
  • the polymer showed low solubility in DMSO and DMAc.
  • a broad 1 H NMR spectrum was obtained in DMSO-d 6 at 100 °C: 7.25, 7.59, 7.70, 7.73, 8.08, 8.38.
  • the molecular weight distribution was measured by gel permeation
  • hydrochloric acid 250 ml_
  • hydrochloric acid 250 ml_
  • the polymer was collected by vacuum filtration using water to wash the polymer.
  • the polymer was washed with concentrated hydrochloric acid followed by water.
  • the damp polymer was washed with hexane followed by methanol and dried in a vacuum oven at 70 °C under nitrogen purge to give 8.35 g (97 % yield) of poly[(2,2'-bis-benzenesulfonyl-4,4'-biphenylene)].
  • the polymer showed low solubility in DMSO and DMAc.
  • a broad 1 H NMR spectrum was obtained in DMSO-d 6 at 120 °C: 7.29, 7.63, 7.73, 7.74, 8.10, 8.41 .
  • the molecular weight distribution was measured by gel permeation chromatography in DMAc: M n 19,400, M w 83,800, M z 244,000; [ ⁇ ] 4.32.
  • Thermo-gravimetric analysis (10 °C/min scan rate) showed an onset of decomposition at 400 °C under air. Differential scanning calorimetry showed a glass transition temperature of 225 °C.
  • the cooled reaction mixture was poured into concentrated hydrochloric acid to precipitate the polymer and the mixture was chopped in a blender to disperse the polymer into particles.
  • the polymer was collected by vacuum filtration using methanol to wash the polymer.
  • the polymer was washed several times with concentrated hydrochloric acid followed by methanol.
  • the damp polymer was dried in a vacuum oven at 80 °C under nitrogen purge to give 2.17 g (100 % yield) of the 95:5 copolymer, poly[(2,2'-bis-benzenesulfonyl-4,4'-biphenylene)-co- (benzenesulfonyl-1 ,4-phenylene)].
  • the polymer showed low solubility in DMSO and DMAc.
  • the cooled reaction mixture was poured into concentrated hydrochloric acid to precipitate the polymer and the mixture was chopped in a blender to disperse the polymer into particles.
  • the polymer was collected by vacuum filtration using methanol to wash the polymer.
  • the polymer was washed twice with concentrated hydrochloric acid followed by methanol.
  • the damp polymer was dried in a vacuum oven at 80 °C under nitrogen purge to give 2.05 g (100 % yield) of the 90:10 copolymer, poly[(2,2'-bis-benzenesulfonyl-4,4'-biphenylene)-co-(benzenesulfonyl-1 ,4- phenylene)].
  • the copolymer (0.5 g) was dissolved in DMAc at 160 °C to give 5.0 weight % solution.
  • the cooled solution was filtered using a glass microfiber syringe filter and poured into a glass film-casting dish, which was placed on a leveled drying stage in a nitrogen-purged drying chamber.
  • the dried film became slightly hazy and lifted free of the dish on its own.
  • the film was further dried at 150 °C in a vacuum oven under nitrogen purge. The film was strong in tension, but was brittle as it broke into pieces when folded over and creased.
  • the copolymer (0.5 g) was dissolved in 1 ,1 ,2,2-tetrachloroethane at room temperature to give 3.2 weight % solution.
  • the solution was filtered using a glass microfiber syringe filter and poured into a glass film-casting dish, which was placed on a leveled drying stage in a nitrogen-purged drying chamber.
  • the film was further dried at 80 °C in a vacuum oven under nitrogen purge. The film had become opaque and was floated free of the dish in water after scoring the edge. The film was not strong in tension and was brittle such that film could not even be folded over.
  • the mixture was extracted several times with dichloromethane.
  • the organic extracts were dried with sodium sulfate, filtered, and evaporated, then the solids were dried in a vacuum oven to give 14.38 g (100 % crude yield).
  • the solids were recrystallized from ethanol after treating with decolorizing carbon to give about 14 g in two crops.
  • the solids were recrystallized from ethanol to give 12.24 g (85 % yield) of 2-benzenesulfonyl-1 ,4- dichlorobenzene.
  • a 1 L round- bottom flask equipped with a stirring bar was charged with copper(l) chloride (25 g, 0.25 moles) and hydrochloric acid (85 mL) to give a dark green solution then chilled to 0 °C in an ice bath.
  • the cold diazonium salt slurry was added slowly to the solution to give immediate gas evolution.
  • the solution was stirred until it warmed to room temperature and evaporated to remove excess hydrochloric acid.
  • the solids were dissolved in water, treated with sodium carbonate to give pH 7, which precipitate residual copper salts, filtered and evaporated to give a tan solid.
  • reaction mixture was diluted with DMAc (20 mL), poured into concentrated hydrochloric acid to precipitate the polymer, and rinsed from the flask with methanol and concentrated hydrochloric acid.
  • the mixture was chopped in a blender to disperse the polymer into particles. The polymer was collected by vacuum filtration and rinsed from the blender jar with methanol, then washed on the filter three times with a mixture of methanol and concentrated hydrochloric acid.
  • the polymer was then washed alternatively with water and methanol several times, and dried in a vacuum oven at 80 °C under nitrogen purge to give 0.41 g (100 % yield) of the 90:10 copolymer, poly[(2,2'-bis-benzenesulfonyl-4,4'-biphenylene)-co-(benzenesulfonyl-1 ,4- phenylene)].
  • the molecular weight distribution was measured by gel permeation chromatography in DMAc: M n 60,100, M w 331 ,000, M z 1 ,600,000; [ ⁇ ] 9.12.
  • Thermo-gravimetric analysis (10 °C/min scan rate) showed an onset of decomposition at 400 °C under air.
  • Differential scanning calorimetry showed a glass transition temperature of 227 °C. This shows that 10 mole percent comonomer had no effect on the glass transition temperature when compared to the homopolymers of Examples 4 and 5, and was in fact higher presumably due to the improved reactivity of the chlorine groups, which also led to higher molecular weights than the copolymers of Examples 6 and 7.
  • the copolymer (0.1 g) was dissolved in 1 ,1 ,2,2-tetrachloroethane to give 1 .1 weight % solution.
  • the solution was poured into a

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PCT/US2010/062199 2009-12-29 2010-12-28 Polyarylene polymers and processes for preparing WO2011090705A2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015040196A (ja) * 2013-08-22 2015-03-02 Jsr株式会社 芳香族ジハライド化合物、重合体、重合体組成物及び成形体

Families Citing this family (3)

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EP2926903A1 (en) * 2014-03-31 2015-10-07 Studiengesellschaft Kohle mbH Process for preparing catalyst loaded polyphenylene particles, the obtained polyphenylene particles and their use as catalysts
US11224158B2 (en) 2019-08-22 2022-01-18 Great Plains Manufacturing, Inc. Metering device for agricultural product
US11206758B2 (en) 2019-08-22 2021-12-28 Great Plains Manufacturing, Inc. Flow tent for an agricultural product bin

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5962631A (en) 1995-07-28 1999-10-05 The Dow Chemical Company 2, 7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers
WO2000053656A1 (en) 1999-03-05 2000-09-14 Cambridge Display Technology Limited Polymer preparation
US6353072B1 (en) 1999-03-05 2002-03-05 Cambridge Display Technology Limited Polymer preparation from boron derivative functional group-containing monomers
US20050239994A1 (en) 2004-03-31 2005-10-27 Litt Morton H Liquid crystal poly(phenylene sulfonic acids)
EP1995265A1 (en) 2006-03-07 2008-11-26 Sumitomo Chemical Company, Limited Polyarylene and process for producing the same
JP2009079214A (ja) 2007-09-04 2009-04-16 Sumitomo Chemical Co Ltd スルホ基を有する重合体の製造方法
EP2065420A1 (en) 2006-09-20 2009-06-03 Sumitomo Chemical Company, Limited Method for producing polyarylene

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5565543A (en) * 1988-02-17 1996-10-15 Maxdem Incorporated Rigid-rod polymers
US5889134A (en) * 1996-11-26 1999-03-30 North Dakota State University Chiral organozinc species for use in asymmetric reactions
AU2003268784A1 (en) * 2002-10-08 2004-05-04 Toyo Boseki Kabushiki Kaisha Polyarylene ether compound containing sulfonic acid group, composition containing same, and method for manufacturing those
JP4661083B2 (ja) * 2004-02-05 2011-03-30 住友化学株式会社 高分子化合物およびその製造方法
US20080287646A1 (en) * 2005-10-13 2008-11-20 Sumitomo Chemical Company, Limited Polyarylene and Method for Producing the Same
JP5040226B2 (ja) * 2006-03-07 2012-10-03 住友化学株式会社 ポリアリーレン及びその製造方法
JP2008285661A (ja) * 2007-04-17 2008-11-27 Sumitomo Chemical Co Ltd スルホン酸基を有するポリマーの製造方法
JP2009275219A (ja) * 2008-04-17 2009-11-26 Sumitomo Chemical Co Ltd ポリアリーレンの製造方法
JP2013515848A (ja) * 2009-12-29 2013-05-09 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリアリーレンアイオノマー性膜

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5962631A (en) 1995-07-28 1999-10-05 The Dow Chemical Company 2, 7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers
WO2000053656A1 (en) 1999-03-05 2000-09-14 Cambridge Display Technology Limited Polymer preparation
US6353072B1 (en) 1999-03-05 2002-03-05 Cambridge Display Technology Limited Polymer preparation from boron derivative functional group-containing monomers
US20050239994A1 (en) 2004-03-31 2005-10-27 Litt Morton H Liquid crystal poly(phenylene sulfonic acids)
EP1995265A1 (en) 2006-03-07 2008-11-26 Sumitomo Chemical Company, Limited Polyarylene and process for producing the same
EP2065420A1 (en) 2006-09-20 2009-06-03 Sumitomo Chemical Company, Limited Method for producing polyarylene
JP2009079214A (ja) 2007-09-04 2009-04-16 Sumitomo Chemical Co Ltd スルホ基を有する重合体の製造方法

Non-Patent Citations (19)

* Cited by examiner, † Cited by third party
Title
"Vogel's Textbook of Practical Organic Chemistry", 1981, LONGMAN (LONDON, pages: 285 - 286
COLON ET AL.: "Journal of Polymer Science, Part A, Polymer Chemistry", vol. 28, 1990, pages: 367
COURTOT ET AL., BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE, vol. 49, 1931, pages 1047 - 1065
COURTOT; LIN, BULL. SOC. CHIM. FR, vol. 49, 1931, pages 1047
COURTOT; LIN, BULL. SOC. CHIM. FR., vol. 49, 1931, pages 1047
H. BORNS: "Annalen der Chemie", vol. 187, pages: 350
HAGBERG; OLSON; SHEARES, MACROMOLECULES, vol. 37, 2004, pages 4748
LOPPINET ET AL., LANGMUIR, vol. 14, 1998, pages 4958 - 4960
LOYDA ET AL., BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 63, 1990, pages 80
MIYAURA ET AL., SYNTHETIC COMMUNICATION, vol. 1 1, 1981, pages 513
MORONI ET AL., MACROMOLECULES, vol. 27, 1994, pages 562
RULKENS ET AL., MACROMOLECULAR: RAPID COMMUNICATIONS, vol. 15, 1994, pages 669 - 676
See also references of EP2519554A4
SRIVASTAVA ET AL., J. MED. CHEM., vol. 18, 1975, pages 798 - 802
ULBRICH ET AL., SOFT MATERIALS, vol. 1, 2003, pages 33 - 52
VANHEE ET AL., MACROMOLECULES, vol. 29, 1996, pages 5136 - 5142
WALLOW ET AL.: "Polymer Preprint", vol. 34, 1993, AMERICAN CHEMICAL SOCIETY, pages: 1009
WANG; QUIRK, MACROMOLECULES, vol. 28, no. 10, 1995, pages 3495
YAMAMOTO, PROGRESS IN POLYMER SCIENCE, vol. 17, 1992, pages 1 153

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015040196A (ja) * 2013-08-22 2015-03-02 Jsr株式会社 芳香族ジハライド化合物、重合体、重合体組成物及び成形体

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